Conductive composition and ceramic electronic component

ABSTRACT

Disclosed is a conductive composition used for a conductor of an electronic component, comprising a metal particle and a metal oxide particle which has an average particle size of 5 to 60 nm, a melting point of 1500° C. or higher, and a content of 0.1 to 10.0 wt % based on the amount of the metal particle. According to the conductive composition, even when the metal particle is made fine, a sintering initiation temperature can be adequately increased, thus a generation of a crack and a de-lamination can be prevented easily and firmly.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a conductive composition usedfor a conductive material of an electronic component, and to a ceramicelectronic component.

[0003] 2. Related Background Art

[0004] It has proceeded to make a thin-layered dielectric and athin-layered electrode corresponding thereto in order to comply withrequirements of miniaturization and capacity enlargement of a capacitor.

[0005] There is a tendency that a metal powder comprised in an electrodepaste used to form an electrode is made fine when making thethin-layered electrode. However, when the metal powder is made fine, asurface energy per unit volume increases and thereby, a sinteringinitiation temperature of the electrode is lowered. Thus, the differencein the sintering initiation temperatures between the electrode and thedielectric is increased. As a result, a crack or a de-lamination easilyoccurs, and reliability of the capacitor is lowered.

[0006] In order to suppress occurrence of the crack or thede-lamination, it is proposed to increase an amount of a compatiblematerial added to the electrode paste (for example, refer to JapanesePatent Application Laid Open No. HEI 7-201223). The compatible materialmeans such ceramics that have the same composition as that of thedielectric or do not deteriorate properties of the dielectric. Inaddition, the sintering initiation temperature of the compatiblematerial is higher than that of the metal powder used for the electrode.The sintering initiation temperature of the electrode can approach thatof the dielectric by increasing the amount of compatible material.

[0007] However, when the amount of compatible material is increased, ametal component per unit volume of the electrode is reduced. Thereby,continuity of the conductive material of the electrode is hindered, andthe electrode effective area in the capacitor decreases. This means thatthe capacitance becomes small even in the same capacitor design.

[0008] On the other hand, a ceramic multilayer insulator also requiresminiaturization and reduction of loss. In order to miniaturize theinsulator, it is necessary to narrow the line width of the electrode andthin the thickness thereof. However, in the case of the above-mentionedconfiguration, the loss of the electrode line increases, and it becomesdifficult to attain the low loss performance. Similarly, in the case ofthe insulator, when there is a big difference in the sinteringinitiation temperatures between the electrode and the ceramics, thecrack or the de-lamination occurs and the reliability is lowered.

[0009] Hence, a study has been done in order to solve the aforementionedproblem. For example, Japanese Patent Application Laid Open No. HEI6-290985 discloses a conductive composition in which an oxide of atleast one element selected among magnesium, zirconium, tantalum and rareearth element is added to a conductive paste made of the metal powder ofnickel powder. In the above-mentioned publication, it is described thata generation of the crack can be prevented because an expansion of thenickel electrode is suppressed in a baking step by use of theabove-mentioned composition.

[0010] Moreover, Japanese Patent Application Laid Open No. 2000-340450discloses the conductive composition in which nickel powder coated witha magnesium oxide layer is compounded. The above-mentioned publicationdescribes that by use of such method, a generation of the crack and thede-lamination can be suppressed by increasing the sintering initiationtemperature of the electrode, and a moisture resistance load propertycan be improved to make a thin layer of the internal electrode.

SUMMARY OF THE INVENTION

[0011] However, the above-mentioned conventional conductive compositionshave a room for improvement in the following points.

[0012] Namely, the conductive composition described in Japanese PatentApplication Laid Open No. HEI 6-290985 has not paid an attention to aparticle size of the added oxide. According to the study by the presentinventors, when the particle size of the oxide used for the conductivecomposition is equal to or bigger than that of the metal powder, thesintering initiation temperature cannot be adequately increased, thusthe crack and the de-lamination will occur. In addition, it is likely todeteriorate the continuity and the surface smoothness of the metal afterbaking.

[0013] Further, in the case of the conductive composition described inJapanese Patent Application Laid Open No. 2000-340450, as mentioned inthis publication, several steps such as evaporation, a coating ofmagnesium compound, and a baking thereafter are required. Thereby, itcauses problems that production steps are increased and a materialmanufacturing cost is enlarged in order to coat the nickel powdersurface with the magnesium layer.

[0014] The present invention is attained in consideration of theproblems imposed on the above-mentioned conventional art. The purpose isto provide a conductive composition for a ceramic electronic componentwhich can adequately increase the sintering initiation temperature evenwhen a fine metal is comprised in the conductive composition, and alsocan obtain the continuity and the surface smoothness of the sinteredmetal after baking. In addition, the ceramic electronic component can beobtained by a cheaper price without any special production steps andfacilities. Moreover, another object of the present invention is toprovide the ceramic electronic component which can effectively realizeminiaturization and thinning by use of the conductive composition.

[0015] The present inventors have made every effort to attain theabove-mentioned objects and found out that the above-described problemsare solved by adding a metal oxide particle to the conductivecomposition, the metal oxide satisfying particular conditions in theaverage particle size and/or BET value. As a result, the inventors haveachieved to accomplish the present invention.

[0016] Namely, a first conductive composition of the present inventionis a conductive composition used for a conductive material of anelectronic component, comprising a metal particle and a metal oxideparticle which has an average particle size of 5 to 60 nm and a meltingpoint of 1500° C. or higher, wherein a content of the metal oxideparticle is 0.1 to 10.0 wt % based on the amount of the metal particle.

[0017] According to the first conductive composition, the metal oxideparticle can exist in a state where the metal oxide particles aredispersed finely and uniformly by comprising the metal oxide particlesatisfying the above-described particular conditions of the averageparticle size and the melting point with a specific content to that ofthe metal particle. Therefore, even when the metal particle is madefine, the sintering initiation temperature can be adequately increased,and the generation of the crack and the de-lamination can be preventedeasily and firmly. Additionally, since the metal oxide particle existsin a state where the metal oxide particle is dispersed finely anduniformly in the metal particle, the continuity and the surfacesmoothness of the sintered metal after baking can be accomplished at ahigher level. Further, a performance of the electronic component can beimproved without increasing the amount of the metal oxide particle thatis a compatible material.

[0018] The first conductive composition preferably further contains abinder resin and a solvent which can dissolve the binder resin. Thus,the conductive composition as a conductive paste can be effectivelyrealized.

[0019] In the above-mentioned first conductive composition, the averageparticle size of the metal oxide particle is preferably 1/3 to 1/80 ofthat of the metal particle. By using such a metal oxide particle, thegeneration of the crack and the de-lamination can be more firmlyprevented.

[0020] Furthermore, a second conductive composition of the presentinvention is a conductive composition used for a conductive material ofan electronic component, comprising a metal particle and a metal oxideparticle which has a BET value (BET specific surface area) of 20 to 200m²/g and a melting point of 1500° C. or higher, wherein the content ofthe metal oxide particle is 0.1 to 10.0 wt % based on the amount of themetal particle.

[0021] According to the second conductive composition, by comprising themetal oxide particle satisfying the above-described particularconditions of the BET value and the melting point in comparison with aspecific content to that of the metal particle, the sintering initiationtemperature can be adequately increased even when the metal particle ismade fine. Thus, the generation of the crack and the de-lamination canbe prevented easily and firmly.

[0022] The above-mentioned second conductive composition preferablyfurther contains the binder resin and the solvent which can dissolve thebinder resin. Thus, the conductive composition as the conductive pastecan be effectively realized.

[0023] In the second conductive composition, the BET value of the metaloxide particle is preferably 5 to 200 times that of the metal particle.By using such a metal oxide particle, the generation of the crack andthe de-lamination can be firmly prevented.

[0024] Furthermore, a ceramic electronic component of the presentinvention comprises a ceramic substrate and a conductive layer which isformed in at least one of inside and outside of the ceramic substrateand comprises the metal particle and the metal oxide particle which hasan average particle size of 5 to 60 nm and a melting point of 1500° C.or higher. The content of the metal oxide particle is 0.1 to 10.0 wt %based on the amount of the metal particle.

[0025] In the ceramic electronic component of the present invention, byforming a conductive layer which comprises the metal oxide particlesatisfying the above-mentioned particular condition of the averageparticle size and the melting point in comparison with a specificcontent to that of the metal particle, a difference in the sinteringinitiation temperature between the conductive layer and the ceramicsubstrate becomes sufficiently small. Therefore, the generation of thecrack and the de-lamination can be prevented easily and firmly.

[0026] Note that the above-described conductive layer of the ceramicelectronic component is obtained by using the first conductivecomposition. However, a similar effect can be obtained when theelectrode is formed by use of the second conductive composition.

[0027] The ceramic electronic component of the present invention ispreferably provided with a capacitor which is formed by comprising theceramic substrate and the conductive layer. Further, in the electrode ofthe capacitor, the metal particle is selected from at least one kindamong nickel and nickel alloys, and the metal oxide particle is an oxidecompound which comprises at least one kind of metals selected frommagnesium, aluminum, titanium and zirconium.

[0028] In addition, the ceramic electronic component of the presentinvention is preferably provided with an insulator which is formed bycomprising the ceramic substrate and the conductive layer. Further, inthe electrode of the insulator, the metal particle is selected from atleast one kind among silver and silver alloys, and the metal oxideparticle is an oxide compound which comprises at least one kind ofmetals selected from magnesium, aluminum, titanium and zirconium.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029]FIG. 1 is a schematic view showing an example of a state of ametal particle and a metal oxide particle comprised in a conductivecomposition of the present invention.

[0030]FIG. 2 is a schematic view showing an example of a state of ametal particle and a metal oxide particle comprised in a conductivecomposition of the prior art.

[0031]FIG. 3 is a schematic sectional view showing a preferableembodiment of a multilayer capacitor according to the ceramic electroniccomponent of the present invention.

[0032]FIG. 4 is a schematic sectional view showing a preferableembodiment of a multilayer insulator according to the ceramic electroniccomponent of the present invention.

[0033]FIG. 5 is a schematic sectional view showing a preferableembodiment of a LC resonator according to the ceramic electroniccomponent of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] Hereafter, preferable embodiments of the present invention aredescribed.

[0035] (Conductive Composition)

[0036] As described above, a conductive composition of the presentinvention comprises a metal particle and a metal oxide particle. Thekind of the metal particle is suitably selected depending on a usage ofthe conductive composition. For example, when a capacitor electrode isformed by using the conductive composition of the present invention,preferably used examples for the metal particle are nickel (Ni) or Nialloys such as Ni—Mn, Ni—Cr, Ni—Co and Ni—Al, and preferably used onesfor the metal oxide particle are oxide compounds of a metal such asmagnesium (Mg), aluminum (Al), titanium (Ti) and zirconium (Zr).Moreover, when an insulator electrode (winding) is formed by using theconductive composition of the present invention, preferably usedexamples for the metal particle are silver (Ag), copper (Cu), palladium(Pd) or alloys thereof, and preferably used ones for the metal oxideparticle are oxide compounds of a metal such as Mg, Al, Ti and Zr. Themetal oxide particle may be a mixture of two or more kinds of the metaloxides, and may be a complex oxide comprising two or more kinds ofmetals.

[0037] The average particle size of the metal oxide particle comprisedin the conductive composition of the present invention is 5 to 60 nm,and more preferably 5 to 50 nm. When the average particle size of themetal oxide particle is less than 5 nm, the sintering initiationtemperature becomes excessively high, and when exceeding 60 nm, thesintering initiation temperature cannot be adequately increased. Thus,in either case, the generation of the crack and the de-lamination cannotbe adequately prevented.

[0038] In addition, the average particle size of the metal oxideparticle is preferably 1/80 to 1/3 of that of the metal particle, andmore preferably 1/80 to 1/10. When the average particle size of themetal oxide is less than 1/80 of that of the metal particle, thesintering initiation temperature becomes excessively high, and whenexceeding 1/3, it gives a tendency that the sintering initiationtemperature cannot be adequately increased.

[0039] Further, in the conductive composition of the present invention,the metal oxide particle may be used which has BET value of 20 to 200m²/g, and preferably 30 to 200 m²/g. BET value of 20 to 200 m²/g issubstantially equivalent to the average particle size of 5 to 60 nm. Themetal oxide particle is accepted as long as at least one of BET valueand the average particle size satisfies the above-mentioned condition.

[0040] Furthermore, BET value of the metal oxide particle is preferably5 to 200 times that of the metal particle. When BET value of the metaloxide exceeds 200 times that of the metal particle, the sinteringinitiation temperature tends to excessively increase, and when beingless than 5 times, the sintering initiation temperature tends to beunable to adequately increase.

[0041] The melting point of the metal oxide particle used in the presentinvention is 1500° C. or higher, and more preferably 1600° C. or higher.When the melting point of the metal oxide particle is less than 1500°C., the metal oxide particle is melted at temperatures that are ageneral sintering temperature (normally 900 to 1350° C.) to produce theceramic electronic component or a sintering temperature of the metalparticle (such as Ni, Ag and alloys thereof). The melting points of thepreferred metal oxides are shown below.

[0042] MgO: 2800° C.

[0043] Al₂O₃: 2050° C.

[0044] TiO₂: 1750° C.

[0045] ZrO₂: 2677° C.

[0046] In the conductive composition of the present invention, thecontent of the metal oxide fine particle is 0.1 to 10.0 wt % based onthe amount of the metal particle. When the content of the metal oxideparticle is less than 0.1 wt % based on the amount of the metalparticle, the sintering initiation temperature cannot be adequatelyincreased, and when exceeding. 10.0 wt %, the sintering cannot proceedadequately. Thus, in either case, the generation of the crack and thede-lamination cannot be sufficiently prevented. In addition, when theconductive composition of the present invention is applied to thecapacitor or the insulator, from the viewpoint of stably securingcapacitance or Q value at a higher level, the content of the metal oxideparticle is preferably 2 to 7.5 wt %, and more preferably 2 to 7 wt %,based on the amount of the metal particle.

[0047] The preferred type of the conductive composition of the presentinvention is a conductive paste. The conductive paste can be suitablyrealized by further compounding a binder resin and a solvent dissolvingthe binder resin in addition to the aforementioned metal particle andthe metal oxide particle; The examples of the binder resin are celluloseresin such as ethyl cellulose, rosin group resin, ployvinyl group resin,butyral group resin, polyester group resin, acryl group resin, epoxygroup resin, polyamide group resin, polyurethane group resin, alkydgroup resin, maleic acid group resin, petroleum group resin, and thelike. Among these, the preferable ones are acryl group resin andcellulose group resin such as ethyl cellulose. Additionally, the solventis not particularly limited as long as it can dissolve theabove-mentioned binder resin, however, the examples are alcohols such asethanol, aromatic hydrocarbons such as toluene and xylene, ethers,ketones, chlorohydrocarbons, and the like. The binder resin and thesolvent may be each used alone or used as a mixture of two or more kindsthereof.

[0048] Moreover, when the conductive composition of the presentinvention is used as the conductive paste, it may further comprise asurfactant, a plasticizer, an antistaic agent, an antifoaming agent, anantioxidant, a slip additive, a curing agent, and the like as additivesif required.

[0049] According to the conductive composition of the present inventionhaving the above-mentioned constitution, even when the metal particle ismade fine, the sintering initiation temperature can be adequatelyincreased, and the generation of the crack and the de-lamination can beprevented easily and firmly.

[0050] Herein, a reason why the above-mentioned effect can be obtainedby use of the conductive composition of the present invention isexplained by referring to the FIG. 1 and FIG. 2. FIG. 1 is a drawingschematically showing the state of the metal particle and the metaloxide particle comprised in the conductive composition of the presentinvention. Further, FIG. 2 is a drawing schematically showing the stateof the metal particle and the metal oxide particle comprised in theconductive composition of the prior art. In each of FIG. 1 and FIG. 2,the reference numeral 1 represents the metal particle, and the referencenumeral 2 represents the metal oxide fine particle.

[0051] In the present invention, by comprising the metal oxide fineparticle 2 which satisfies the above-described particular conditions ofthe average particle size and/or BET value, and the melting point in theconductive composition, as shown in FIG. 1, the metal oxide particle 2can be dispersed finely and uniformly in the metal particle 1. Hereby,the metal particle 1 can exist against the other adjacent metal particle1 through the metal oxide fine particle 2, and the contact among themetal particles 1 themselves can be decreased. As a result, thesintering initiation temperature can be increased, and the generation ofthe crack and the de-lamination can be prevented.

[0052] On the contrary, as shown in FIG. 2, when the average particlesize or the BET value of the metal oxide particle 2 is equal to or morethan that of the metal particle 1, a ratio of the portion where the onlymetal particle 1 exists to that of the total composition becomes larger,thus the sintering initiation temperature cannot be adequatelyincreased.

[0053] As described above, the conductive composition of the presentinvention is very useful for the conductive material of the ceramicelectronic component, thus is suitably used for the capacitor describedbelow, the insulator, the LC resonator, or the ceramic electroniccomponent which is made by combining those parts with other elements.

[0054] Next, the ceramic electronic component of the present inventionis described in detail.

[0055]FIG. 3 is a schematic sectional view showing a preferableembodiment of a multilayer capacitor according to the ceramic electroniccomponent of the present invention. The multilayer capacitor 301 shownin FIG. 3 is provided with a capacitor element body 310 and a pair ofoutside electrodes 304, 304. The capacitor element body 310 is made byalternately laminating a dielectric layer 302 and a conductive layer 303for an inside electrode. The pair of outside electrodes 304, 304 isarranged on the two surfaces opposing to each other in the capacitorelement body 310, and are each arranged in the end portion sides of theconductive layer 303. The conductive layers 303 are respectivelyconducted to one of the outside electrodes 304, 304 every two layers.Namely, in one conductive layer 303, the end portion thereof exposes toone surface of the above-mentioned two surfaces, and the end portion ofthe conductive layer 303 adjacent to the above-described conductivelayer 303 exposes to another surface of the above-mentioned twosurfaces, and each inside electrode 303 is electrically connected to oneof the outside electrodes 304, 304. The shape of the capacitor elementbody 310 is not particularly limited, however, is usually a rectangularsolid. Besides, a dimension of the capacitor element body 310 is notparticularly limited, so the appropriate dimension may be determined inaccordance with the usage. Generally, it is about (0.4 to 5.6 mm)×(0.2to 5.0 mm)×(0.2 to 1.9 mm).

[0056] The dielectric layer 302 is formed by use of dielectric materialssuch as BaTiO₃, TiO₂, CaZrO₃, MnO and Y₂O₃. These dielectric materialsmay be used alone or used in combination of two or more kinds.

[0057] The conductive layer 303 is formed by use of the conductivecomposition of the present invention. In this case, the conductivecomposition preferably comprises the metal particle of Ni or Ni alloyand the metal oxide which includes at least one kind of the metal oxideparticle selected from Mg, Al, Ti and Zr.

[0058] The outside electrode 304 is formed by use of the conductivematerial. Such conductive materials are, for example, Ag, Ni, Cu, In, Gaor alloys thereof. As for the outside electrode 304, can be applied anyone of printed film, plated film, evaporated film, ion-plated film,sputtered film, and multilayer film thereof.

[0059] Hereafter, an example of producing the multilayer capacitor 301is explained. At first, by using the above-described dielectricmaterials, a dielectric sheet is made by use of pulling method, doctorblade method, reverse roll coater method, gravure coater method, screenprinting method, gravure printing method, and the like. Meanwhile, theconductive paste is prepared by mixing the metal particle, the metaloxide particle, the binder resin and the solvent followed by kneadingthem. Then, the prepared conductive paste is coated on the surface ofthe dielectric sheet into the pattern of the conductive layer 303 by useof screen printing method, gravure printing method, offset printingmethod, and the like. Thereafter, a plural of dielectric sheets on whichthe conductive paste is coated are multilayer followed by a pressurebonding. Then, the multilayer forming product is baked at apredetermined temperature (preferably 900 to 1350° C.) in the air oratmosphere containing oxygen. Thus, the capacitor element body 310 canbe obtained, which forms the inside electrode inside of the ceramicsubstrate. Subsequently, the paste for the outside electrode comprisingthe conductive material is coated on the predetermined surface of thecapacitor element body 310, and baked to obtain the multilayer capacitorwhich forms the outside electrodes 304, 304 electrically connected tothe conductive layer 303.

[0060] According to the above-mentioned embodiment, by use of theconductive composition of the present invention, the generation of thecrack and the de-lamination can be prevented even when the dielectriclayer 302 is thin-layered. More specifically, the multilayer capacitorhaving high reliability can be realized even when the thickness of thedielectric layer 302 is 0.5 to 1.0 μm.

[0061] Note that in the above-mentioned embodiment, the conductivecomposition of the present invention was used for the conductivematerial of the conductive layer 303 being the inside electrode.However, the conductive composition of the present invention can be alsoused for the conductive material of the outside electrode 304.

[0062]FIG. 4 is a schematic sectional view showing a preferableembodiment of the multilayer insulator according to the ceramicelectronic component of the present invention. The multilayer insulator401 shown in FIG. 4 is provided with a chip body 410 and a pair ofoutside electrode 405, 405 which are arranged on the two surfacesopposing to each other in the chip body 410. The chip body 410 isintegrated by alternately laminating an insulator layer 402 and theconductive layer 403. In the chip body 410, the conductive layer 403 isformed in a pattern, and a through-hole which puts the adjacentconductive layer 403 in a continuity state is formed at a predeterminedposition in the insulator layer 402. Thereby, a coil is constituted. Inaddition, both end portions of the coil are each electrically connectedto one of outside electrodes 405, 405. The external form and thedimension of the chip body 410 are not particularly limited but can besuitably selected depending on the usage. Generally, the external formis nearly a rectangular solid shape, and the dimension may be about (1.0to 5.6) mm×(0.5 to 5.0) mm×(0.6 to 1.9) mm.

[0063] The insulator layer 402 is formed by use of an insulatingmaterial. The examples of such insulating material are magnetic powders,and ceramic group magnetic powder, metal group magnetic powder, andalloy group magnetic powder are preferably used. The insulatingmaterials may be used alone, or used in combination of two or morekinds.

[0064] The conductive layer 403 is formed by use of the conductivecomposition of the present invention. In this case, the conductivecomposition preferably comprises the metal particle of Ag or Ag alloyand the metal oxide which comprises at least one kind of the metal oxideparticle selected from Mg, Al, Ti and Zr. As for Ag alloy, thepreferable one is Ag-Pd alloy comprising Ag of 95 wt % or more.

[0065] The adjacent conductive layers 403 are electrically connected toeach other through the through-hole, and a continuity path formed in thethrough-hole is also made by use of the conductive composition of thepresent invention. In addition, a winding pattern (closed magneticcircuit pattern) of the coil made by the conductive layer 403 which isformed as described above is not particularly limited, however, it isusually a spiral pattern. A winding number and a pitch of the coil maybe suitably selected depending on the usage.

[0066] The outside electrode 405 is formed by use of the conductivematerial. Such conductive materials are, for example, Ag, Ni, Cu oralloys thereof. As the outside electrode 405, any one of printed film,plated film, evaporated film, ion-plated film, sputtered film, andmultilayer film thereof can be applied.

[0067] Hereafter, an example of producing the multilayer insulator 401is explained. At first, a paste for dielectric layer, a paste forconductive layer, and a paste for outside electrode are respectivelyprepared. Subsequently, the paste for dielectric layer and the paste forconductive layer are alternately coated using a method such as printingmethod, transcription method and green sheet method. Then, the obtainedmultilayer body is cut into the predetermined dimension followed bybaking. Thus, obtained is a multilayer forming product of the insulatorlayer 402 and the conductive layer 403. In this case, the through-holeis formed by laser, punching, or the like, and by packing the paste forconductive layer into the through-hole, the adjacent dielectric layers403 are conducted to form the coil. The chip body 410 is made by bakingthe multilayer forming product which is obtained in the above-mentionedmethod. Furthermore, by coating the paste for outside electrode on thepredetermined surface of the chip body 410 followed by baking, theoutside electrodes 405, 405 are formed to electrically connect to theend portion of the coil. Thus, the multilayer insulator 401 is obtained.

[0068] According to the above-mentioned embodiment, by use of theconductive composition of the present invention, the generation of thecrack and the de-lamination can be prevented even when the insulatorlayer 402 is thin-layered. More specifically, the multilayer insulatorhaving high reliability can be realized even when the thickness of theinsulator layer 402 is 2 to 10 μm.

[0069] Note that in the above-mentioned embodiment, the conductivecomposition of the present invention was used for the conductivematerial of the conductive layer 403. However, the conductivecomposition of the present invention can be also used for the conductivematerial of the outside electrode 405.

[0070]FIG. 5 is a schematic sectional view showing a preferableembodiment of a LC resonator according to the ceramic electroniccomponent of the present invention. A LC resonator 501 shown in FIG. 5is made by sandwiching a multilayer body with two GND patterns 505, 506from both sides in the laminating direction. The multilayer body isformed by arranging a coil 503 and a capacitor 504 on a differentdielectric layer 502 respectively inside a multi-layered substrate whichis constituted by a plural of dielectric layers 502.

[0071] The GND pattern 505 is an electrode for trimming when theresonance frequency of the LC resonator 501 is adjusted. The trimming isperformed by selecting a position where a coil pattern 507 is notpatterned as described later. Thereby, when not only the GND pattern 505but also the dielectric layer thereunder is cut out through thetrimming, a property defect and the like caused by a damage of a coilpattern 507 can be prevented.

[0072] The coil pattern 507 of the coil 503 and a capacitor electrodepattern 508 of the capacitor 504 are each formed by use of theconductive composition of the present invention. The coil pattern 507 isprovided on the nearest side to the GND pattern 505 based on thelaminating direction. Meanwhile, the capacitor electrode pattern 508 ofthe capacitor 504 is provided on the farthest side to the GND pattern505 based on the laminating direction. In addition, the coil pattern 507is patterned in some areas on the dielectric layer 502. On the otherhand, the capacitor electrode pattern 508 is patterned almost over thewhole area of the dielectric layer 502.

[0073] Through the forgoing configuration, the LC resonator 501 can berealized in which the coil 503 and the capacitor 504 are built-inbetween two GND patterns 505 and 506. Further, by using the conductivecomposition of the present invention for the component materials of thecoil pattern 507 and the capacitor electrode pattern 508, a highreliability is accomplished even when each layer is thin-layered.

EXAMPLES

[0074] Hereinafter, the present invention is more specifically explainedbased on the examples and the comparative examples. However, the presentinvention is not limited to the following examples.

Example 1

[0075] The multilayer capacitor was produced in accordance with thefollowing procedures.

[0076] At first, Al₂O₃ particle (average particle size: 50 nm, BETvalue: 30 m²/g) of 0.1 wt % and vehicle of 70 wt % composed of ethylcellulose resin and terpineol were added to Ni particle (averageparticle size: 0.4 μm). The contents of Al₂O₃ particle and vehicle werebased on the amount of Ni particle. Then, they were kneaded to obtainthe conductive paste.

[0077] Meanwhile, a ceramic slurry having the formulation in which Y₂O₃of 0.5 mol % was added to the composition of 100 mol % comprising BaTiO₃of 97.5 mol %, CaZrO₃ of 2.0 mol % and MnO of 0.5 mol %, was coated by adoctor blade method on a band shaped carrier film made of syntheticresins such as polyester and polypropyrene. Subsequently, after drying,a ceramic green sheet was peeled off from the carrier film to make aband shaped ceramic green sheet of 10 μm thick. Then, the ceramic greensheet was punched into the site of 200 mm length and 200 mm width.

[0078] Onto one of the main surfaces of the obtained ceramic greensheet, the aforementioned conductive paste was printed in a pattern ofthe inside electrode layer by use of a screen printing equipment. Theceramic green sheet with the above-mentioned paste was multilayer sothat the conductive layers might form four layers, and the multilayerforming product was obtained.

[0079] Next, the obtained multilayer forming product was heated at 300°C. in the air or at 500° C. in the atmosphere of oxygen/nitrogen of 0.1Pa to perform a treatment of removing the binder. Subsequently, themultilayer forming product was baked for 2 hours at 1260° C. in theatmosphere of oxygen/nitrogen of 10⁻⁷ Pa, furthermore, was subjected toa reoxidation treatment at 900° C. in the atmosphere of oxygen/nitrogenof 10⁻² Pa to obtain the ceramic sintered material. After baking, anindium-gallium paste was coated on each end surface of the obtainedceramic sintered material, then formed was the outside electrode whichwas electrically connected to the inside electrode layer.

[0080] The external dimension of the multilayer ceramic capacitorobtained above was 1. 6 mm width, 3.2 mm length, 1.0 mm thick, thethickness of the dielectric layer was 3 μm, and that of the conductivelayer was 1.2 μm.

Examples 2 to 5, Comparative Examples 1 to 2

[0081] In the Examples 2 to 5 and Comparative Examples 1 to 2, themultilayer capacitors were each produced similarly to the Example 1except that the conductive pastes were prepared by setting the contentsof Al₂O₃ in the conductive pastes as shown in Table 1.

Examples 6 to 9, Comparative Examples 3 to 4

[0082] In the Examples 6 to 9 and Comparative Examples 3 to 4, themultilayer capacitors were each produced similarly to the Example 1except that the metal oxide particles shown in Table 1 were used insteadof Al₂O₃ having the average particle size of 50 nm and the contents ofthe metal oxide particles in the conductive pastes were set to 5.0 wt %based on the amount of the Ni particle. TABLE 1 Metal oxide particleMetal Average particle particle BET Content size value Content Kind (wt%) Kind (nm) (m²/g) (wt %) Comparative Ni 100 Al₂O₃ 50 30 0.05 Example 1Example 1 Ni 100 Al₂O₃ 50 30 0.1 Example 2 Ni 100 Al₂O₃ 50 30 2.0Example 3 Ni 100 Al₂O₃ 50 30 5.0 Example 4 Ni 100 Al₂O₃ 50 30 7.5Example 5 Ni 100 Al₂O₃ 50 30 10.0 Comparative Ni 100 Al₂O₃ 50 30 12.0Example 2 Comparative Ni 100 Al₂O₃ 100 26 5.0 Example 3 Example 6 Ni 100Al₂O₃ 60 20 5.0 Example 7 Ni 100 Al₂O₃ 5 200 5.0 Comparative Ni 100Al₂O₃ 2 250 5.0 Example 4 Example 8 Ni 100 MgO 13 100 5.0 Example 9 Ni100 TiO₂ 30 50 5.0

[0083] (Reliability Evaluation of the Multilayer Capacitor)

[0084] The capacitance at 1 kHz was measured for each of multilayercapacitors obtained above. In addition, it was checked whether or notthe generation of the crack and the de-lamination was observed byanalyzing the inside of the capacitor. The obtained result is shown inTable 2. TABLE 2 Occurrence of crack Capacitance (nF) and de-laminationComparative Example 1 25.5 yes Example 1 26.3 no Example 2 26.0 noExample 3 27.5 no Example 4 26.0 no Example 5 25.4 no ComparativeExample 2 23.8 no Comparative Example 3 24.1 yes Example 6 25.5 noExample 7 25.9 no Comparative Example 4 24.4 no Example 8 27.3 noExample 9 26.7 no

[0085] As shown in Table 2, in the multilayer capacitors in the Examples1 to 9, the capacitance value could be secured over the predeterminedvalue, and the generation of the crack and the de-lamination was notobserved, thus a high reliability was achieved.

[0086] On the contrary, in the multilayer capacitors in the ComparativeExamples 1 to 4, the capacitance value was low, and the generation ofthe crack and the de-lamination was observed.

Example 10

[0087] The multilayer insulator was produced in accordance with thefollowing procedure.

[0088] At first, Al₂O₃ particle (average particle size: 13 nm, BETvalue: 100 m²/g) of 0.1 wt % and vehicle of 30 wt % composed of ethylcellulose resin and butylcarbinol were added to Ag particle (averageparticle size: 0.5 μm) The contents of Al₂O₃ particle and vehicle werebased on the amount of Ag particle. Then they were kneaded to obtain theconductive paste. Meanwhile, the insulator paste comprising aborosilicate glass particle and an Al₂O₃ particle was prepared.

[0089] Next, by using the above-mentioned conductive paste and theinsulator paste, the conductive layer and the insulator layer weremultilayer by a printing method. In this case, the through-hole wassuitably formed, which conducts the adjacent conductive layers, and themultilayer body was obtained in which the coil shaped conductor having aturn number of 3 was formed inside thereof. This multilayer body wasbaked at 900° C. for 10 minutes, then the multilayer insulator forming aspiral shaped winding therein was obtained whose inside conductor was100 μm width and 15 μm thick, and whose external dimension was 1.6mm×0.8 mm×0.4 mm.

Examples 11 to 14, Comparative Examples 5 to 6

[0090] In the Examples 11 to 14 and Comparative Examples 5 to 6, themultilayer insulators were each produced similarly to the Example 10except that the contents of Al₂O₃ in the conductive pastes were set asshown in Table 3.

Examples 15 to 18, Comparative Examples 7 to 8

[0091] In the Examples 15 to 18 and Comparative Examples 7 to 8, themultilayer insulators were each produced similarly to the Example 10except that the metal oxide particles shown in Table 3 were used insteadof Al₂O₃ having the average particle size of 13 nm and the contents ofthe metal oxide particles in the conductive pastes were set to 5.0 wt %based on the amount of Ag particle. TABLE 3 Metal oxide particle MetalAverage particle particle BET Content size value Content Kind (wt %)Kind (nm) (m²/g) (wt %) Comparative Ag 100 Al₂O₃ 13 100 0.05 Example 5Example 10 Ag 100 Al₂O₃ 13 100 0.1 Example 11 Ag 100 Al₂O₃ 13 100 2.0Example 12 Ag 100 Al₂O₃ 13 100 5.0 Example 13 Ag 100 Al₂O₃ 13 100 7.5Example 14 Ag 100 Al₂O₃ 13 100 10.0 Comparative Ag 100 Al₂O₃ 13 100 12.0Example 6 Comparative Ag 100 Al₂O₃ 100 26 5.0 Example 7 Example 15 Ag100 Al₂O₃ 60 20 5.0 Example 16 Ag 100 Al₂O₃ 5 200 5.0 Comparative Ag 100Al₂O₃ 2 250 5.0 Example 8 Example 17 Ag 100 ZrO₂ 25 80 5.0 Example 18 Ag100 TiO₂ 30 50 5.0

[0092] (Reliability Evaluation of the Multilayer Insulator)

[0093] The Q value at 500 kHz was measured for each of 10 multilayerinsulators obtained above. In addition, it was checked whether or notthe generation of the crack and the de-lamination was observed byanalyzing the inside of the insulator. The obtained result is shown inTable 4. TABLE 4 Occurrence of crack and Q value de-laminationComparative Example 1 31.2 yes Example 10 30.9 no Example 11 30.4 noExample 12 29.0 no Example 13 27.8 no Example 14 27.2 no ComparativeExample 2 26.0 no Comparative Example 3 30.7 yes Example 15 29.9 noExample 16 27.5 no Comparative Example 4 26.3 no Example 27 28.4 noExample 18 28.7 no

[0094] As shown in Table 4, in the multilayer insulators in the Examples10 to 18, the Q value could be secured over the predetermined value, andthe generation of the crack and the de-lamination was not observed, thusa high reliability was achieved.

[0095] On the contrary, in the multilayer insulators in the ComparativeExamples 5 to 8, the Q value was low, and the generation of the crackand the de-lamination was observed.

What is claimed is:
 1. A conductive composition which is used for a conductor of an electronic component, comprising a metal particle and a metal oxide particle which has an average particle size of 5 to 60 nm and a melting point of 1500° C. or higher, wherein a content of the metal oxide particle is 0.1 to 10.0 wt % based on the amount of the metal particle.
 2. A conductive composition according to claim 1, further comprising a binder resin and a solvent dissolving the binder resin.
 3. A conductive composition according to claim 1, wherein the average particle size of the metal oxide particle is 1/3 to 1/80 of that of the metal particle.
 4. A conductive composition which is used for a conductor of an electronic component comprising a metal particle and a metal oxide particle which has a BET value of 20 to 200 m²/g and a melting point of 1500° C. or higher, wherein a content of the metal oxide particle is 0.1 to 10.0 wt % based on the amount of the metal particle.
 5. A conductive composition according to claim 4, further comprising a binder resin and a solvent dissolving the binder resin.
 6. A conductive composition according to claim 4, wherein the BET value of the metal oxide particle is 5 to 200 times that of the metal particle.
 7. A ceramic electronic component comprising: a ceramic substrate; and a conductive layer which is formed in at least one of the inside and outside of the ceramic substrate and comprises a metal particle and a metal oxide particle which has an average particle size of 5 to 60 nm and a melting point of 1500° C. or higher, wherein a content of the metal oxide particle is 0.1 to 10.0 wt % based on the amount of the metal particle.
 8. A ceramic electronic component according to claim 7, which comprises a capacitor formed by including the ceramic substrate and the conductive layer, wherein, in the conductive layer, the metal particle is at least one kind selected from nickel and nickel alloys, and the metal oxide particle is an oxide compound comprising at least one kind of metals selected from magnesium, aluminum, titanium and zirconium.
 9. A ceramic electronic component according to claim 7, which comprises a insulator formed by including the ceramic substrate and the conductive layer, wherein, in the conductive layer, the metal particle is at least one kind selected from silver and silver alloys, and the metal oxide particle is an oxide compound comprising at least one kind of metals selected from magnesium, aluminum, titanium and zirconium. 